Abstract
A new paper filler, comprising microcapsules with a urea-formaldehyde resin shell and a porous calcium silicate core (UF@CS-MC), was prepared by in situ polymerization. UF@CS-MC, which has good retention in the paper matrix and enhances both whiteness and opacity, provides a low-cost alternative to titanium dioxide, which is traditionally used as a filler for Bible paper. Conditions for the preparation of UF@CS-MC, including core to coating ratio, emulsification time, emulsifier concentration, stirring rate, pH and polymerization time, were investigated and optimized. The UF@CS-MC filler was characterized using a variety of analytical techniques, including optical microscopy, scanning electron microscopy, Fourier-transform infrared spectroscopy and laser Raman spectroscopy. Incorporation of UF@CS-MC into Bible paper produced a notable improvement in both whiteness (10.75 %) and opacity (13.97 %). Compared with titanium dioxide, UF@CS-MC as Bible paper filler achieved a 20 % improvement in filler retention and a 49.4 % reduction in cost.
Funding source: the National Key R&D Program of China
Award Identifier / Grant number: SQ2024YFD2200039
Funding source: he National Natural Science Foundation of China
Award Identifier / Grant number: 22408044
Funding source: the China Postdoctoral Science Foundation
Award Identifier / Grant number: 2024M761877
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Research ethics: Not applicable.
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Informed consent: Not applicable.
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Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.
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Use of Large Language Models, AI and Machine Learning Tools: None declared.
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Conflict of interest: All other authors state no conflict of interest.
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Research funding: This work was supported by the National Natural Science Foundation of China (22408044), the National Key R&D Program of China (SQ2024YFD2200039), the China Postdoctoral Science Foundation (2024M761877).
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Data availability: The datasets generated and/or analyzed during the current study are available from the corresponding author on reasonable request.
References
Adel, A.M., Ahmed, N.M., Diab, M.A., and Selim, M.M. (2016). The influence of TiO2/CC core/shell pigments on the properties of paper sheets. Powder Technol. 291: 437–447, https://10.1016/j.powtec.2016.01.007.10.1016/j.powtec.2016.01.007Search in Google Scholar
Chen, Z., Zhang, W., Yuan, Z., Wang, Z., Ma, R., and Chen, K. (2022). Preparation of strawberry chitosan composite microcapsules and their application in textiles. Colloids and Surf. A: Physicochem. Eng. Aspects 652: 129845, https://10.1016/j.colsurfa.2022.129845.10.1016/j.colsurfa.2022.129845Search in Google Scholar
Fortuna, M.E., Harja, M., Bucur, D., and Cimpeanu, S.M. (2013). Obtaining and utilizing cellulose fibers with in-situ loading as an additive for printing paper. Materials 6: 4532–4544, https://10.3390/ma6104532.10.3390/ma6104532Search in Google Scholar PubMed PubMed Central
Hill, C.G., Hedren, A.M., Myers, G.E., and Koutsky, J.A. (1984). Raman spectroscopy of urea–formaldehyde resins and model compounds. J. Appl. Polym. Sci. 29: 2749–2762, https://10.1002/app.1984.070290906.10.1002/app.1984.070290906Search in Google Scholar
Huang, L., Chen, K., Lin, C., Yang, R., and Gerhardt, R.A. (2010). Fabrication and characterization of superhydrophobic high opacity paper with titanium dioxide nanoparticles. J. Mater. Sci. 46: 2600–2605, https://10.1007/s10853-010-5112-1.10.1007/s10853-010-5112-1Search in Google Scholar
Huo, J.H., Peng, Z.G., and Feng, Q. (2019). Synthesis and properties of microencapsulated phase change material with a urea-formaldehyde resin shell and paraffin wax core. J. Appl. Polym. Sci. 137: 48578, https://10.1002/app.48578.10.1002/app.48578Search in Google Scholar
John, E. and Stephan, D. (2021). Calcium silicate hydrate-in-situ development of the silicate structure followed by infrared spectroscopy. J. Am. Ceram. Soc. 104: 6611–6624, https://10.1111/jace.18019.10.1111/jace.18019Search in Google Scholar
Li, T., Liang, J., Cao, M., Guo, X., Xie, X., and Du, G. (2016). Re-elucidation of the acid-catalyzed urea-formaldehyde reactions: a theoretical and 13C-NMR study. J. Appl. Polym. Sci. 133, https://doi.org/10.1002/app.44339.Search in Google Scholar
Li, L., Zhang, M., Song, S., Yang, B., Wu, Y., and Yang, Q. (2018). Preparation of core/shell structured silicate composite filler and its reinforcing property. Powder Technol. 332: 27–32, https://10.1016/j.powtec.2018.03.037.10.1016/j.powtec.2018.03.037Search in Google Scholar
Li, Y., Dai, H., Wan, L., and Zhu, Z. (2023). Surface sizing application of waterborne epoxy resin on low basis weight paper. BioResources 7: 5–14, https://10.15376/biores.7.1.5-14.10.15376/biores.7.1.5-14Search in Google Scholar
Lin, C.-C. and Shen, P. (2016). Pressure-induced metastable phase transformations of calcium metasilicate (CaSiO3): a Raman spectroscopic study. Mater. Chem. Phys. 182: 508–519, https://10.1016/j.matchemphys.2016.07.065.10.1016/j.matchemphys.2016.07.065Search in Google Scholar
Mao, H., Cao, X., Guo, M., Jiang, C., and Chen, D. (2024). Study on the repair effect of self-healing cementitious material with urea-formaldehyde resin/epoxy resin microcapsule. Buildings 14: 2201, https://10.3390/buildings14072201.10.3390/buildings14072201Search in Google Scholar
Mujica, M., Tutuncuoglu, G., Shetty, P.P., Mohabir, A.T., Woods, E.V., Breedveld, V., Behrens, S.H., and Filler, M.A. (2020). The geode process: hollow silica microcapsules as a high surface area substrate for semiconductor nanowire growth. ACS Appl. Nano Mater. 3: 905–913, https://10.1021/acsanm.9b02553.10.1021/acsanm.9b02553Search in Google Scholar
Ogur, E., Botti, R., Bortolotti, M., Colombo, P., and Vakifahmetoglu, C. (2021). Synthesis and additive manufacturing of calcium silicate hydrate scaffolds. J. Mater. Res. Technol. 11: 1142–1151, https://10.1016/j.jmrt.2021.01.090.10.1016/j.jmrt.2021.01.090Search in Google Scholar
Peng, J., Chen, X., Zhang, J., Essawy, H., Du, G., and Zhou, X. (2022). Characterization on the copolymerization resin between bayberry (myrica rubra) tannin and pre-polymers of conventional urea-formaldehyde resin. Forests 13: 624, https://10.3390/f13040624.10.3390/f13040624Search in Google Scholar
Qi, F., Sun, J., Zhu, G., Li, H., Wu, Y., Li, S., Yang, C., Zheng, J., and Zhang, Y. (2022). Recycling of blast furnace slag to prepare calcium silicate hydrate by mechanical-chemical co-activation and its application to calcium silicate fireproof board. Process Saf. Environ. Prot. 165: 1–12, https://10.1016/j.psep.2022.06.062.10.1016/j.psep.2022.06.062Search in Google Scholar
Qiu, Y., Cao, S., Chen, F., You, S., and Zhang, Y. (2020). Synthesis of calcium silicate as paper filler with desirable particle size from desilication solution of silicon-containing waste residues. Powder Technol. 368: 137–148, https://10.1016/j.powtec.2020.04.042.10.1016/j.powtec.2020.04.042Search in Google Scholar
Reczulski, M., Pospiech, P., Troszczyńska, K., and Bieńkowska, M. (2024). Impact of air jet impingement technology on the strength of tissue paper. BioResources 19: 1190–1208, https://10.15376/biores.19.1.1190-1208.10.15376/biores.19.1.1190-1208Search in Google Scholar
Ren, S., Wang, C., Guo, L., Xu, C., Wang, Y., Sun, C., Cui, H., and Zhao, X. (2021). Preparation and sustained-release performance of PLGA microcapsule carrier system. Nanomaterials 11: 1758, https://10.3390/nano11071758.10.3390/nano11071758Search in Google Scholar PubMed PubMed Central
Song, S., Zhang, M., He, Z., Li, J.Z., and Ni, Y. (2012). Investigation on a novel fly ash based calcium silicate filler: effect of particle size on paper properties. Ind. Eng. Chem. Res. 51: 16377–16384, https://10.1021/ie3028813.10.1021/ie3028813Search in Google Scholar
Song, S., Zhen, X., Zhang, M., Li, L., Yang, B., and Lu, P. (2018). Engineered porous calcium silicate as paper filler: effect of filler morphology on paper properties. Nord. Pulp and Pap. Res. J. 33: 534–541, https://10.1515/npprj-2018-3045.10.1515/npprj-2018-3045Search in Google Scholar
Steinhof, O., Scherr, G., and Hasse, H. (2015). Investigation of the reaction of 1, 3-dimethylurea with formaldehyde by quantitative on-line NMR spectroscopy: a model for the urea-formaldehyde system. Magn. Reson. Chem. 54: 457–476, https://10.1002/mrc.4274.10.1002/mrc.4274Search in Google Scholar PubMed
Verma, A.K., Suresh, S., and Mohta, D. (2022). Economical and efficient use of fly ash for newsprint paper quality improvement. BioResources 13: 5765–5777, https://10.15376/biores.13.3.5765-5777.10.15376/biores.13.3.5765-5777Search in Google Scholar
Wang, X., Xie, W., Li, T., Ren, J., Zhu, J., Han, N., and Xing, F. (2020). Molecular dynamics study on mechanical properties of interface between urea-formaldehyde resin and calcium-silicate-hydrates. Materials 13: 4054, https://10.3390/ma13184054.10.3390/ma13184054Search in Google Scholar PubMed PubMed Central
Xu, S., Xu, P., Zhao, P.-Q., and Du, Y.-T. (2022). Effect of different size ratio and filling method on the characteristics of calcium silicate-filled paper. BioResources 17: 4196–4205, https://10.15376/biores.17.3.4196-4205.10.15376/biores.17.3.4196-4205Search in Google Scholar
Yu, P., Kirkpatrick, R.J., Poe, B., McMillan, P.F., and Cong, X. (2004). Structure of calcium silicate hydrate (C-S-H): near-mid-and far-infrared spectroscopy. J. Am. Ceram. Soc. 82: 742–748, https://10.1111/j.1151-2916.1999.tb01826.x.10.1111/j.1151-2916.1999.tb01826.xSearch in Google Scholar
Zhang, X. and Long, Z. (2019). Preparation and properties of tungsten-doped VO2 microcapsule intelligent temperature-control packaging paper. Prog. Org. Coat. 131: 219–226, https://10.1016/j.porgcoat.2019.02.030.10.1016/j.porgcoat.2019.02.030Search in Google Scholar
Zhang, D.-X., Li, B.-X., Zhang, X.-P., Zhang, Z.-Q., Wang, W.-C., and Liu, F. (2016). Phoxim microcapsules prepared with polyurea and urea-formaldehyde resins differ in photostability and insecticidal activity. J. Agric. Food Chem. 64: 2841–2846, https://10.1021/acs.jafc.6b00231.10.1021/acs.jafc.6b00231Search in Google Scholar PubMed
Zorba, T., Papadopoulou, E., Hatjiissaak, A., Paraskevopoulos, K.M., and Chrissafis, K. (2008). Urea-formaldehyde resins characterized by thermal analysis and FTIR method. J. Therm. Anal. Calorim. 92: 29–33, https://10.1007/s10973-007-8731-2.10.1007/s10973-007-8731-2Search in Google Scholar
Supplementary Material
This article contains supplementary material (https://doi.org/10.1515/npprj-2025-0007).
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Articles in the same Issue
- Frontmatter
- Bleaching
- A new strategy for biological enzyme bleaching: combined effects of laccase, xylanase, and mannanase in the bleaching of softwood kraft pulp – a synergistic effect of enzymes
- Mechanical Pulping
- Characterization of the low consistency pulp refining conducted by the plates with different bar-groove width ratios
- Paper Technology
- On the influence of macro-scale stress variations on the dynamic dewatering of water-saturated polymer fibre networks
- Effects of dispersion hydrophobized MgO nanoparticles in low polarity solvent on aged paper
- Preparation and properties of effective low-cost composite filler for bible paper
- Paper Physics
- Normal and shear delamination of paperboards
- Micro-CT analysis of creased and folded multilayer cardboard
- Paper Chemistry
- Preparation of MgO/CaCO3 nanocomposites and their deacidification properties for paper documents
- Effects of sequential plasma modification and alkali treatment applied to cellulose fibers on the properties of the paper
- Coating
- Production of nano silver and nano silica coated paper to be used in active packaging
- Insights into bibliometric review for natural coatings for paper-based food packaging: trends, perspectives, and future directions
- RSM optimization of spray-coating parameters to enhance paper strength using cellulose nanocrystals extracted from young coconut husks
- Chemical Technology/Modifications
- NSSC pulp treatment with the Fenton reaction: fiber modification for reduced energy consumption in papermaking
- Other
- Fenton degradation of biologically pre-treated pulp and paper effluent using zero-valent iron from commercial steel wool
- Corrigendum
- Corrigendum to: Preparation and synthesis of water-soluble chitosan derivative incorporated in ultrasonic-assistant wheat straw paper for antibacterial food-packaging